EP0123087B1 - Verfahren zur Herstellung heterocyclischer Phenylether - Google Patents

Verfahren zur Herstellung heterocyclischer Phenylether Download PDF

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Publication number
EP0123087B1
EP0123087B1 EP84102568A EP84102568A EP0123087B1 EP 0123087 B1 EP0123087 B1 EP 0123087B1 EP 84102568 A EP84102568 A EP 84102568A EP 84102568 A EP84102568 A EP 84102568A EP 0123087 B1 EP0123087 B1 EP 0123087B1
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EP
European Patent Office
Prior art keywords
reaction
methyl
formula
compounds
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84102568A
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German (de)
English (en)
French (fr)
Other versions
EP0123087A1 (de
Inventor
Ulrich Dr. Dipl.-Chem. Kussmaul
Johannes Dr. Dipl.-Chem. Becherer
Reinhard Dr. Dipl.-Chem. Handte
Rolf Dr. Dipl.-Chem. Müller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanofi Aventis Deutschland GmbH
Original Assignee
Cassella AG
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Publication date
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D235/26—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2

Definitions

  • Lewis acids or strong non-oxidizing mineral acids or organic acids are used as acids.
  • Suitable mineral acids are e.g. As phosphoric acid or hydrogen halide, especially hydrogen chloride.
  • Suitable organic acids are e.g. B. trifluoroacetic acid or p-toluenesulfonic acid. Based on the starting compounds 11 or IV, the acid is used in a catalytic to equimolar amount.
  • Volatile acids, such as hydrogen halides, in particular hydrogen chloride are preferred because, after the reaction has ended, they are increased by increasing the temperature and / or by blowing out with an inert gas, such as, for example. As nitrogen, can be easily removed from the reaction mixture. Gaseous acids are passed through the reaction mixture in a weak stream during the reaction.
  • the process according to the invention is carried out in a suitable solvent or solvent mixture or preferably without a solvent.
  • the solvents used must be inert to the reactants.
  • water-insoluble aromatic hydrocarbons and halogenated hydrocarbons such as. B. toluene, o-, m-, p-xylene, especially in the form of the technical xylene mixture, and chlorobenzene.
  • polar aprotic solvents e.g. B.
  • acid amides such as dimethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone and hexamethylphosphoric triamide, also dimethyl sulfoxide or nitriles such as acetonitrile or propionitrile can be used as solvents.
  • the reaction temperatures are between 50 and 300 ° C, preferably at 100 to 200 ° C and, if no solvent is used, preferably above the melting point of compound 111. At reaction temperatures above the boiling point of the solvent used, the reaction is carried out in a closed vessel.
  • the process is preferably carried out without the addition of an acid. In this case, it is often advantageous to carry out the reaction at a relatively low temperature in order to prevent the hydrogen halide formed during the reaction from escaping too quickly from the reaction mixture.
  • the hydrogen halide escaping from the reaction mixture during the reaction can be carried out in a known manner with the aid of standard apparatus, e.g. B. in water or dilute alkali, absorbed and used for other purposes.
  • the molar ratio of the reactants II: III or IV: III or (II + IV): III can be varied within wide limits. It is possible to work with equimolar amounts. An excess of compounds III is favorable. of at least 5 mol%. However, it is also possible to work with a double molar to 5-fold molar excess of compounds of the formula III.
  • the molar ratio of the reactants II: III or IV: III or (II + IV): III is therefore normally 1: (1.05 to 5), preferably 1: (1.05 to 2). Using a larger than 5-fold molar excess of compound III is of no advantage.
  • the process according to the invention is generally carried out in such a way that the dihydroxybenzene III, if appropriate in a solvent and if appropriate with an acid, is initially introduced and warmed to the reaction temperature and the compound II or IV or a mixture of the compounds II and IV is advantageously added with stirring.
  • the addition of an acid is not necessary, since after the addition of compound II a vigorous development of hydrogen halide begins shortly after the reaction temperature has been reached.
  • the hydrogen halide escaping from the reaction mixture be it the excess of hydrogen halide introduced or hydrogen halide released during the reaction, is absorbed in a known manner.
  • the order in which the reactants are added is of minor importance; the reactants can also be added simultaneously, or the reactants of the formula 11 or IV can be introduced.
  • the response times are short in all cases and range from 10 minutes to 12 hours. Surprisingly, they are each significantly shorter than in the known processes according to EP 924.
  • the progress of the reaction can easily be followed by thin layer chromatography.
  • the method according to the invention is usually under a protective gas, such as. B. an inert gas, carbon dioxide or nitrogen. The use of nitrogen as a protective gas is preferred.
  • the mixture is cooled and worked up in a suitable manner.
  • the residue is normally filtered off with suction and introduced into water, with the addition of lye (such as, for example, sodium or potassium hydroxide solution) or a buffer (such as, for example, disodium hydrogenphosphate), ensuring that a pH of 7 is maintained .
  • lye such as, for example, sodium or potassium hydroxide solution
  • a buffer such as, for example, disodium hydrogenphosphate
  • a in formula 1 is N- (C 1 -C 4 ) alkyl
  • A is preferably N-CH 3 .
  • the compounds of formula I are valuable precursors for effective biocides, e.g. B. for herbicides, in particular for those as proposed in US Pat. No. 4,130,413.
  • valuable selective herbicides are obtained, for example, from the compounds of formula 1 by reaction with 2-halogenopropionic acid derivatives, such as esters and amides, in a manner known per se.
  • 2-halogenopropionic acid derivatives such as esters and amides
  • the starting compounds of formula II can be z. B. from the corresponding 2-mercapto or 2-oxo compounds by halogenation or else from the 2-amino compounds by diazotization and subsequent Sandmeyer reaction (see, for example, BCA 59,396 j; Am. Chem. J. 21 (1899 ), 111).
  • the starting compounds 111, pyrocatechol, resorcinol and hydroquinone are known.
  • the use of hydroquinone is preferred.
  • the starting compounds of the formula IV are formed in the reaction of compounds II with compounds III as undesirable by-products per se, in particular when the compounds II are present in excess in the reaction.
  • the batch is immediately introduced while still hot in finely divided form into 1.5 l of well-stirred water, neutralized with a little sodium hydroxide solution and boiled at 100 ° C. for 10 minutes. It is filtered off hot and washed with a little hot water. After drying at 70 ° C. and a pressure of approx. 20 mbar, 273.5 g (98.5% of theory) of 4- (6'-chlorobenzthiazolyl-2'-oxy) phenol of melting point 174 to 177 ° C. are obtained. Recrystallization from toluene gives a product with mp. 178 to 179 ° C.
  • the xylene-moist paste is stirred with 100 ml of water, adjusted to pH 7 with about 1 to 1.5 g of Na 2 HP0 4 and the xylene is removed by steam distillation. It is suctioned off hot and washed with about 150 ml of hot water. After drying at 70 ° C. and about 20 mbar, 46.3 g (88% of theory) of 4- (6'-chlorobenzoxazolyl-2'-oxy) phenol with an mp of 181 to 183 ° C. are obtained.
  • reaction temperature is increased to 135 to 140 ° C. when the example is repeated, the reaction time is extended to approximately 8 hours. If, in a repetition of the example, the reaction is carried out by refluxing, then it is no longer possible to carry out the reaction properly without the addition of an acid, because the hydrogen chloride formed from the 2,6-dichlorobenzoxazole at the reflux temperature of the xylene (approx. 144 ° C) escaped from the reaction mixture too quickly.
  • the batch is cooled to room temperature and suction filtered.
  • the xylene-moist paste is stirred with 1 liter of water, adjusted to pH 7 with about 10 to 15 g of Na 2 HP0 4 and then the xylene is removed by steam distillation. It is suctioned off hot and washed with 1.5 l of hot water. After drying, 475 g of 4- (6'-chloro-benzoxazolyl-2'-oxy) phenol remain 95%, mp 175 to 180 ° C, corresponding to 450 g 100%, that is 86% of theory. Bisether content approx. 4 to 5%, hydroquinone content approx. 0.5%. Hydroquinone crystallizes out of the filtrate on cooling.
  • the xylene-moist paste is stirred into 1 liter of water, adjusted to pH 7 with about 10 to 15 g of Na 2 HPO 4 and the xylene is removed by steam distillation. It is suctioned off hot and washed with 1.5 l of hot water. After drying, about 475 g of 4- (6'-chlorobenzoxazolyl-2'-oxy) phenol 95% strength, mp. 175 to 180 ° C, corresponding to about 450 g of 100% strength, that is 86% of theory . Hydroquinone crystallizes out of the filtrate on cooling.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
EP84102568A 1983-03-28 1984-03-09 Verfahren zur Herstellung heterocyclischer Phenylether Expired EP0123087B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19833311285 DE3311285A1 (de) 1983-03-28 1983-03-28 Verfahren zur herstellung heterocyclischer phenylether
DE3311285 1983-03-28

Publications (2)

Publication Number Publication Date
EP0123087A1 EP0123087A1 (de) 1984-10-31
EP0123087B1 true EP0123087B1 (de) 1987-07-01

Family

ID=6194902

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84102568A Expired EP0123087B1 (de) 1983-03-28 1984-03-09 Verfahren zur Herstellung heterocyclischer Phenylether

Country Status (5)

Country Link
US (1) US4564682A (enrdf_load_stackoverflow)
EP (1) EP0123087B1 (enrdf_load_stackoverflow)
JP (1) JPS59181264A (enrdf_load_stackoverflow)
CA (1) CA1217494A (enrdf_load_stackoverflow)
DE (2) DE3311285A1 (enrdf_load_stackoverflow)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1318488B1 (it) 2000-04-21 2003-08-25 Ausimont Spa Fluorovinileteri e polimeri da essi ottenibili.
JP2013053556A (ja) 2011-09-05 2013-03-21 Aisan Industry Co Ltd 蒸発燃料処理装置

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933841A (en) * 1971-05-24 1976-01-20 Ciba-Geigy Corporation 2-Phenoxy, -phenylthio-, and -phenyl-amino-benzoxazoles having an isothiocyano substituent
BE792402A (fr) * 1971-12-07 1973-06-07 Ciba Geigy Composes heterocycliques azotes et medicaments anthelminthiqueset antimicrobiens qui en contiennent
DE2640730C2 (de) * 1976-09-10 1983-08-25 Hoechst Ag, 6230 Frankfurt Benzoxazolyloxy- und Benzothiazolyloxy-phenoxy-Verbindungen und diese enthaltende herbizide Mittel
DE2738963A1 (de) * 1977-08-30 1979-03-15 Hoechst Ag Heterocyclische phenylaether und verfahren zu ihrer herstellung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
C. FERRI: Reaktionen der organischen Chemie, Georg Thieme Verlag, 1978, 395-99 *

Also Published As

Publication number Publication date
CA1217494A (en) 1987-02-03
EP0123087A1 (de) 1984-10-31
JPH0369345B2 (enrdf_load_stackoverflow) 1991-10-31
DE3464493D1 (en) 1987-08-06
JPS59181264A (ja) 1984-10-15
DE3311285A1 (de) 1984-10-11
US4564682A (en) 1986-01-14

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